Photochemistry of allyloxybenzophenones: a pseudo-Paternò-Büchi rearrangement accompanied by hydrogen transfer induced 1,5-cyclization
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[(DPEPhos)(bcp)Cu]PF6: A General and Broadly Applicable Copper-Based Photoredox Catalyst
Published on: May 21, 2019
Raúl Pérez-Ruiz1, Olga Hinze, Jörg-M Neudörfl
1Department of Chemistry, University of Cologne, Greinstrasse, 4, D-50939, Cologne, Germany.
Abstract:
The solution photochemistry of the ortho allyloxy-substituted benzophenone has been investigated in detail. Product analysis revealed formation of a diastereomeric mixture of dihydrobenzofuran derivatives by cyclization via a short-lived intermediate 1,5-biradical and an unusual acetal by a pseudo-Paternò-Büchi rearrangement. The latter reaction pathway was supported by means of laser flash photolysis, where a long-lived intermediate with a maximum absorption band at 380 nm was observed. Besides, theoretical calculations (TD-DFT) of this UV-transient resulted in a band with maximum intensity at 390 nm showing a good correlation between experimental results and theoretical calculations. For comparison, the meta-substituent substrate was also investigated showing preferred triplet-triplet energy transfer.
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